Fungitoxic agents



United States Patent 3,275,501 FUNGITOXIC AGENTS Gerhard Schrader,Wuppertal-Cronenberg, and Paul-Emst Frohberger, Burscheid, Germany,assignors to Farben- 3,275,501 Patented Sept. 27, 1966 comparison to theknown 'S,S,"S,-trimethyl trit-hiolthlono-phosphoric acid ester, thecompounds'to be applied according to the invention possess asubstantially increased fungitoxiczeifect, which is not limited only tofungi of the 2:51:21 clitliy-egnrgzrigt'aiszllllschaft, Leverkusen,Gerplythiumhgrollllp as is the case with 0,0,0-trimethyl- 9 t v NoDrawing. Filed June 3, 1964, Ser. No. 372,391 3 2323 51gggeg z g iigifgi g; R l iz t Claims priority, application Germany June 4 19.63 p a Ives0 e F 907 types as well as to numerous otherpythopathogemc fungi. 6Claims 167 22) In contrast to the products used for the same purpose 1Oaccordmg to the state of the art, the 'dialkyl-thionothio'l- The presentinvention relates to and has as its object phosphoric and -phosphonicacid esters of the invention iungitoxic agents based onthionothiolphosphoric and thus possess the advantage of a higherfungitoxic degree -phosphon1c acid esters of the formula of efiect aswell as a broader spectrum of activity. This R10 8 behaviouriscompletely surprising and could not be fore- \{J, seenin any way. 3Moreover, the pythium-active 0,0,0-trimethyl-thiono- Ra phosphoric acidester itself shows only a small degree of in whi h, R t d f a lower lkdi l, R f a stability even-at roomtemperature. The compound deloweralkyl, alkenyl, alkoxy or an optionally substituted composes especiallywhen finely distributed Over a large lower alkylmercapto group, while Ris an optionally subsurfacc -sccllulcsc) with luminescence phcncmcnastituted lower alkyl radi al. and development of smoke. In contrast, the0,0,S-tri- As subsftituents for the radicals R and R principal y 0r yyland h y examples are halogen atoms, cyano, thioeyano, hydro y,ethyl-thionoth-iolphosphoridcacid esters tobe used accordalkoxy andalkylmercapto groups. ing to the invention, for example,,prove to.-be.substantially In German published application No. 1,073,237 and'inmore Stable- US. patent specification No. 3,080,274, the 0,0,0-tri- Thec p s according o theinvention'arc, moremethylthionophosphoric acidester h s already b e d over, distinguished to some extent by anextraordinarily scribed as being fungicidally active, butspecifically-active low'toxicity to -warm -blooded animals'as well as ahigh against fungi of the pythium group. It is also known tolerance byhigher plants. They are, therefore, emifrom the above-mentioned US.patent specification that n y suited for ppli a ion gainst f ngous plandisease the corresponding 0,0,0-triet-hyl compounds possesses as well asfor combating undesired fungous growth. substantially weaker fungitoxicproperties when compared The prodllctsrnav be pplied alone 01 in Co binio with the trimethyl ester, and *itsrapplication as a fungicide withother plant protective or:pest control agents such or plant protectiveagent is therefore not considered in as fungic de i secti llcmatflcides,herbicides, and practice. cultivating aids, e.g. fertilizers and soilstructure improvers. Furthermorqthe 0,9,0 trimethyl phosphoric acidesterThey can, moreover,'be'preparedwith various preparation ortheS,S;S,-trimethyltrithiol-phosphorous acid ester and assistants,'such assolvents, pulverulent extending, wetting the S,S',S-trimethyltrithiolthi-ono-phosphoric acid ester or adhesive agents, dyestufis andemulsifiers. Theycan are indicated as being inactive against plantpathogenic be employed as concentrates, or extended with suitable fungiin the cited U.S. patent specification. 40 inert materials, as powders,'granulates, pastes, solutions, I It has now surprisingly been :foundthat thionothio'lemulsions or-suspensions. They are-thusappliedbyatomphosphoric and -phosphonic :acid esters of the aboveizing,"spraying, fumigating, sprinkling, scattering, dustmentioned structureare distinguished by an especially ing, pouring, injectingor in adry,moist, wet-or-slurry strong fungitoxic activity and are thusoutstandingly dressing'prccess. -suited for combating undesired fungusgrowth. The following examples are given for the purpose of Thephosphoric acid esters :of :the present invention illustrating theinvention in more' detail. -f1?he compounds can be prepared by reactionswelllknownin'the prior art. to be used according to the invention andindicated-below The reactions are ill'ustrated by US. Patents 2,494,284,are characterised in the individual examples .by'the cor- 2,5 86565 5and 2,61 1,'l-28. responding Roman numerals:

TABLE I .Preparation Constitution Preparation -'Constituti0n L .CHaO s n-i cmo "s a a CHaO sCH3 oHso sOrHr .III .CflHsO S IV CzHrO S ozHao \SCH3CnHuO scaHa V CHaO S VI CzHsO S P P CHaO \SCH2CN CzHsO \SCH:SCN vrr01130 S vrn C2H60 s CHaS SCHs CHsS SCHa The fungitoxic activity and thebreadth of the spectrum of activity of the compounds to be employedaccording to the inventionare tested with the aid of the agar platetest. For this purpose, .the preparation in question is dissolved inacetone in a proportion of 1:1 and these solutions are added to apotato-dextrose-agar in such an amount that a concentration of 0.1%active agent is present. potato-dextrose-agar is previously liquified byheating and after thorough shaking with the preparation under sterileconditions, is then poured into Petri dishes.

After the substrate-active agent mixture solidifies, 8 difierentphytopathogenic fungi are inoculated from ,pure cultures in discs of mm.diameter. The action of the following fungi was tested:

(1) Corticium rolfsii (2) Sclerotinia sclerotiorum .(3) Verticilliumalboatrum (4) Thielaviopsis basicola (5) Phytophthora cactorum (6)Fusarium culmorum (7) Fusarium oxysporum (8) Fusarium solani After,three. days incubation at C. the evaluation proceeds by evaluating themycelium growth or determina- The' TABLE IContlnued PreparationConstitution Preparation Constitution No. No.

IX (EH50 S X 01130 S 1 CzHsS SClHi CHaS OH: XI CZHiO s XII CzHbO s CaHsSCH; CaHsS CnHs 5 xrn canto s xrv 0,1150 s t CN-CHz- S CH=CCH;Cl-CHzCHz-S CH-(E-CH: 7 CH: 7 i 7 CH3 3 Xv 0,1150 s xvr 0310 s iCNCHz-CH:S CH= |J-CH1 CHsO SCHzOH XVII CHsO S XVIII CHaO S a 4 CHaOSCHaCI CHaO SCHaSCzHs XIX nctnvo s xx CHBO s nCaHrO SCH: iCaH'IO SCH:

Example] 1 35 111, VI, VIII, X, XI, XII, X111 and XV indicatcd-in TableI completely inhibit any myceli-urn growth.

Example 2 'The applicability of the compounds according to the inventionfor combating fungous plant diseases isvtested and shown by thefollowing experiments: For testing as soil-treating agents againstphytopathogenic soil fungi, the preparations in question are first diluted with tale to.

an active agent concentration of about 5%, and then, with the aid offinely divided quartz sand, extended to 0.5% and in this form admixedwith the soil. 'For the tests.

preparations.

tion of the inhibiting action of the individual compounds. mentalresults obtained are .assembled in the following a It is thus shownthat, for example, the Preparations I, II, Table H. 7

TAB E 11 No. of healthy plants in percent 3 wks. alter sowing andinfection Preparation Active agent with- No. Active agent (Constitution)concentration v inmgJlitre soil Rhizocto'nia Puthium solani ultimum I(EH30 S 2.5 a y 5 CHaQ SCH: 50

fat peas almost exclusively I are carried out in: the

healthy plants is determined as a measure of the protective actionachieved by the t In this way the plant tolerance of the indit vidualactive agents becomes apparent by a normal growth of the plantsprotected before infection. The experi- TABLE II-Continued N o. healthyplants in percent 3 wks. after sowing and infection Preparation Activeagent with N 0. Active agent (Constitution) concentration in mgJlitresoil Rhizoctonla Pythium solam' ultimum XX CHaO S 5 76 y 68 i3 3% iCaHzOSCH: 100 72 Example 3 We claim:

1. A method for controlling phytopathogenic fungi The sometimessubstantial distant elfect of the active agents employed according tothe invention in the soil is tested with the aid of the following testarrangement:

-70 milligrams of Preparation I, in the form of a 10% pumice gritgranulate with a particle size of 0.5 to 1.5 mm. diameter, areintroduced 5 cm. deep in a sandy soil. On the soil surface an agar plateinJa Petri dish inoculated with Rhizoctonia solani is placed with itsopening downwards, so that the fungus does not come into direct contactwith the soil. A distant fungicidal effect through the 5 cm. high layerof soil becomes evident leading to a strong inhibition of the fungusgrowth on the agar plate.

Example 4 Preparation I, moreover, shows a substantial stability againsthydrolytic influences:

After standing for 4 days a 10% slurry in water emulsified with 10%alkylaryl polyglycol ether, maintains an unaltered activity againstRhdizoctonia as is shown by vegetation experiments in the greenhouse.The preparation possesses a considerable stability also in the soil, asis apparent from the following experiment:

Sterilised Fruhstorfer standard soil is treated with various amounts ofPreparation I in the form of a 0.5% talcquartz sand-scattering powder,onepart of the soil is inoculated immediately with pure Rhizoctoniasolani cultures and simultaneously sown with peas, the other partinoculated and sown in the same way three weeks later. The test resultsobtained are shown in Table III.

which comprises applying to said fungi a fungicidally eifective amountof a compound of the formula CHQO 4.-A method for controllingphytopathogenic fungi which comprises applying to said fungi afungicidal amount of a phosphorus containing compound of the a sO czHsO5. A method for controlling phytopathogenic fungiv which comprisesapplying to saidfungi a fungicidal From the experimental data given inTable III it is tpparent that the fungicidal effect of the preparationac- :ording to the invention in the soil remains practically malteredfor 3 weeks similarly to the known control ,gentpentachloronitrobenzene.

amount of a phosphorus containing compound formula for lower alkylhaving up 9 10 6. A method for controlling phytopathogenic fungi2,911,335 11/1959 Gilbert 167--22 which comprises applying to said fungia fungicidal 2,931,755 4/1960 Birum 167-22 amount of a phosphoruscontaining compound of the 2,941,920 6/1960 Willard et a1 16722 formula2,967,123 1/1961 Richter 167-22 S 5 3,047,459 7/1962 Perini et a1.167-22 3,144,384 8/1964 Aichenegg 16722 3,156,718 10/1964 Lorenz e161260-461 OTHER REFERENCES References Cited by the Examiner OrganicInsectofungicides, Zhur. Obschei Khim, 30; UNITED STATES PATENTS 10193-203 (1960), abstracted in English in Chem. Ab- 2,494,2s4 1/1950Cassady etal 260 461 was, 223216423221 (1960)- 2,586,655 2/1952 Hook eta1. 260461 2,611,728 9/1952 Bartlett et a1. 16722 LEWIS GOTTS f f2,856,325 10/1958 Scott et a1 167 -22 15 SHEP K-R0SE,Ass1stantExammer-

1. A METHOD FOR CONTROLLING PHYTOPATHOGENIC FUNGI WHICH COMPRISESAPPLYING TO SAID FUNGI A FUNGICIDALLY EFFECTIVE AMOUNT OF A COMPOUND OFTHE FORMULA